FR2577566A1 - CATIONIC BITUMINOUS EMULSIONS AND GRANULATE-EMULSION SUSPENSIONS - Google Patents

Abstract

BITUMINOUS CATIONIC EMULSION AND MIXTURES OF THIS EMULSION WITH AGGREGATES. THIS EMULSION CONTAINS APPROXIMATELY 30 TO 80 BY WEIGHT OF BITUMEN, ABOUT 0.1 TO 10 BY WEIGHT OF AN EMULSIONING AGENT CONSISTING OF A REACTION PRODUCT OF A POLYAMINE WITH A COMPOUND OF THE GROUP OF UNSATURATED FATTY ACIDS EPOXIDIZED. CC AND THEIR ESTERS, WITH WATER FOR COMPLEMENT TO 100 BY WEIGHT, THE EMULSION IS AT A PH OF 2 TO 7. THIS EMULSION CAN BE MIXED WITH AGGREGATES OF VARIOUS TYPE FOR COATING OF ROADS.

Description

The present invention relates to bituminous emulsions

  perfected, more precisely to medium-breaking cationic emulsions, mixing quality, and

  road surfacing and sealing mixtures of the above type

  quick-release granula- emulsion board. It relates more particularly to new emulsifying agents for cationic bituminous emulsions of the oil-in-water type, of the quality

  for mixing, without solvent or with solvent, these emulsifying agents

  being reaction products of monoamines and / or poly-

  amines and certain vegetable oils or esters of epoxidized fatty acids. In road surfacing work, four main processes are observed to achieve a correct mix of bitumen and aggregate: (1) the heated and fluid asphalt (asphalt cement) is mixed with the previously dried granulate; (2) the pre-dried granulate is mixed with the asphalt diluted with a hydrocarbon solvent (fluxed asphalt, cut product) at room temperature; (3) mixing the granulate with an asphalt emulsion, for example an oil-in-water emulsion, obtained by vigorous stirring of asphalt and water in the presence of an emulsifying agent; and (4) mixing a fine granulate with water and an asphalt emulsion and optionally fillers such as cement or hydrated lime in a roadside coating apparatus, and immediately applying to the surface of

  the road to regenerate. This process is known as coating

by suspension or dispersion.

  Due to the rising costs of energy and soil

  hydrocarbon products, and ecological considerations, emulsified asphalt is increasingly used. Depending on the nature of the agent

  emulsifier used, anionic or cationic emulsions are obtained.

  picnics. In anionic emulsions, the asphalt droplets are negatively charged; in cationic emulsions, the asphalt droplets carry positive charges and migrate to the cathode when an electric field is applied. On-road experiments have shown that cationic emulsions are easier to apply than anionic emulsions and remedy many of the disadvantages of the latter, for example, unpredictable fracture and poor asphalt binding to the surface.

  granulite, leading to a drive. Because of the attrac-

  Electrostatic interaction between positively charged asphaltic droplets and negatively charged aggregate surfaces, cationic bitumen emulsions are deposited more rapidly, and stronger bonds between the bitumen and the granulate are achieved. In general, depending on the characteristics of the mixture and

  the breaking speed, the bituminous aqueous emulsions

  are classified as fast-breaking emulsion (ERR), medium-break emulsion (ERM) and slow-release emulsion (ERL). The breaking speed is determined by the type and quantity of agents

  emulsifiers and the pH of the solution of the cationic surfactant

  Picnic. In the case of fast-breaking emulsions, used primarily

  mainly for the repair of old wearing courses, the emulsion is applied on the existing surface and the aggregate is spread over it, and after compression, the road can be opened to the traffic shortly after the application of the new coating (tightness by gravillions, etc.). The medium-break emulsions are mixed with the granulate prior to use for road construction, and the slow-break emulsions can be mixed with the granulate and stored for

  long durations without breaking on the surface of the granulate.

  In practice, slurry coating mixtures are prepared from (1) a mineral aggregate consisting of a fine stone aggregate and / or a mineral filler, and (2) about 15 to 25% by weight of the aggregate, a slow-breaking, mixing quality emulsion containing about 50 to 75% by weight of a bituminous residue (usually asphalt), with a further addition of about 5 to 25% water relative to dry aggregate weight, in order to achieve the consistency of suspension. Usually, to obtain suspensate coating compositions, dense aggregates such as granite crushing sand, limestone crushing sand, dolomite crushing sand and blast furnace slag are combined with the bituminous emulsions. . These aggregates have dimensions such that all passes through a sieve with a mesh size of 4.76 mm and even 2.00 mm, with 15 to 20% passing through a sieve with a mesh size of 0.074 mm,

  as described in ASTM C136.

  The use of suspension coating as a road coating and maintenance technique was first designed for use with aqueous-bituminous emulsions

  anionic. A suspension coating mixture is a

  Intimate mixture of an emulsified bituminous material and a fine aggregate held in stable suspension until applied to the road surface. The emulsion of the suspension coating mixture must be of the oil-in-water type. In such a mixture with a granulate, the aqueous emulsion form of the bituminous material has

  usually preferred because it is less dangerous

  and more economical to use than hot mix asphalts or fluxed (solvent containing). In addition, the emulsion

  can be stored, transported and applied at temperatures

  much lower eratures, which avoids the use of a

  heating coil to maintain the bitumen-granulate mixture in usable form. Although these advantages are recognized by all, this type of product has not been universally accepted because of the disadvantages encountered in aqueous-bituminous emulsions

of the prior art.

  More recently, cationic bitumen emulsions have been used which overcome many of the disadvantages of

anionic emulsions.

  The cationic emulsions are obtained by using

  various nitrogenous organic compounds such as amines

  fatty diamines, fatty triamines,

  fatty amines, fatty imidazolines, reaction products

  of all these compounds with ethylene oxide, and ammo-

  The fatty radical of these compounds may have various chemical structures, and the raw materials for the preparation of these amines may be obtained from a variety of sources, for example petroleum raffinate, synthetic materials, and the like.

  animal and vegetable fats, fish oil and tall oil.

  Amidoamines suitable for use as emulsifiers

  are described in United States Patents

  3,230,104 and 3,097,174. Combinations of monoamines and trisamines

  fatty amines are described in U.S. Patent 3,738,852; fatty diamines are described in U.S. Patents 3,728,278 and 3,581,101;

  fatty quaternary and diquaternary salts and their modifications.

  US Pat. Nos. 3,220,953, 3,867,162, 3,764,359, 3,956,524, and 3,466,247, and fatty imidazolines are described in the US Pat.

of America 3,445,258.

  In general, cationic emulsions prepared using fatty amines, fatty diamines, amidoamines

  fat, etc. are unstable when mixed with granular

  siliceous or calcareous lats. There is a rapid break on the surface of the aggregate with an increase in rigidity. At this point, mixing becomes impossible to work. To solve this problem, it is common practice to use fluxed asphalt in place of asphalt cement for mix-grade, medium-breaking asphalt emulsions. Although the emulsions

  fluxes prepared with these emulsifiers also break down

  When mixed with the granulate, a solvent (a hydrocarbon oil such as naphtha, kerosene, diesel oil, etc.) decreases the viscosity of the asphalt and facilitates the work of the granulate-asphalt mixture. After placing the mixtures, the solvent evaporates and the final final gangue of granulate-asphalt is obtained. However, in recent years, the price of solvents has increased considerably, and it is also sought to reduce pollution, so that emulsifying agents suitable for cationic emulsions of

  the quality of the mixture does not contain any solvent.

  The aqueous-bituminous cationic emulsions are themselves relatively stable and the stability of the emulsion

  can be increased by means of various and well known additives. Toute-

  Most cationic bituminous emulsions are rapidly deposited on the surface of the granulate when it comes into contact with the emulsion. The bitumen of a cationic aqueous-bituminous emulsion is deposited due to the attraction between the charges of the bitumen droplets and the charges of the aggregate. The fast breaking effect of bituminous cationic emulsions has a considerable advantage in road construction, for example sealing coatings because roads can be opened to traffic shortly after the application of the coating. Although the rate of deposition of asphalt from the emulsion can be controlled for example to a certain extent, the time required

  for a full deposition is never very long and therefore

  common practice is to combine the cationic emulsion with the aggregate at the road construction site, either at

  surface of the road itself, either in a mobile mixer

  rapidly spreading the granulate-emulsion mixture. Because of the charge attraction mechanism, the rate of deposition of the bituminous materials from the cationic emulsion is closely related to the generally negatively charged surface of the aggregate or filler. Thus, although a particular cationic bituminous emulsion may have the desired properties for use with certain aggregates, the same cationic emulsion may not have the desired properties when used with very finely divided total free surface milled materials. strong. The rapid deposition characteristics of cationic bitumen emulsions frequently make it impossible to use these emulsions with a fine granulate in the form of

  suspension for example in the projection application or the application

  Towed frame cation. Therefore, because the slurry coating mix must be well mixed, well pumped, well spread, must not harden on application and, after breaking, must behave well it is particularly desirable to be able to influence the break time of the suspension with the various aggregates used. The use of quaternary ammonium salts of tallow and tallow diquaternary diammonium salts for the preparation of emulsions suitable for suspension coating, a solvent-free application, is described in US Pat. 764,359 and the use of a quaternary amine obtained by reaction of epichlorohydrin, trimethylamine and nonylphenol to

  solvent-free mixtures is described in US Pat.

United States of America 3,956,524.

  Recently, the reaction products of polyamines with certain tall oil-derived C21 dicarboxylic acids, C22 tricarboxylic acids and sulfonated fatty acid acids have been described in U.S. Patents 4,447,269. 4,450,011 and 4,462,840 as emulsifiers

  for fast-breaking cationic emulsions for

  suspension coatings or for cationic emulsions

  quality asphalt for medium breaking blends.

  The general object of the present invention is the discovery of other general-purpose emulsifying agents for bituminous emulsions of the oil-in-water type, of the quality for mixing, with and without solvent. These emulsifiers are suitable for mixing quality emulsions and fast-breaking cationic emulsions for road paving in suspension. The invention also comprises a series of novel fatty amino-amino-amidoamines and imidazolines obtained as a reaction product of vegetable oils or epoxidized fatty acid esters and polyamines, and which are suitable for use as carriers. emulsifiers for cationic emulsions of

oil-in-water type.

  - It has actually been found that unlike amidoamines and imidazolines obtained by condensation of acids

  to a chain length of C12-C22 with polyethylene glycol

  amines such as diethylenetriamine, which give emulsions

  fast-breaking cationic products, the reaction products of poly-

  Amines with epoxidized vegetable oils or epoxidized fatty acid esters provide emulsions capable of yielding cationic asphalt emulsions of medium-breaking blend quality as well as fast-breaking asphalt emulsions. Solventless asphalts as well as asphalts up to 12% by volume can be used for emulsion formation.

  a hydrocarbon oil. Emulsions prepared with

  Condensation feeds according to the invention behave as emulsions prepared with condensation products of polyamines and dicarboxylic acids to C21 derived from tall oil, acids

  C22 tricarboxylic or sulphonated fatty acids.

  Epoxidized vegetable oils or epoxidized fatty acid esters used in the preparation of emulsifiers

  cationic compounds according to the invention are obtained from natural oils

  glycerides such as soybean oil, linseed oil, or

  esters such as alkyl oleates or alkyl esters of tall oil or animal fats which have been epoxidized with peracetic acid or perbenzoic acid. These

  Oxiranes are more commonly used as plasticisers and stabilizers.

  leaflets for polyvinyl chloride or as reagents for

  epoxy resins. The epoxidized acids or esters may also

  derive from hydrochloric acids or fatty esters. For example, the emulsifiers according to the invention can be prepared from the epoxidized triglyceride of oleic acid (I).

CH3 (CH2) 7CH - CH (CH2) 7C - O - 2 (I)

O a

H3 (CH) 7CH - H (CH2) 7C--O - CH

CH3 (CH2) 7C - (CH) CHH2) 7C - O - CH2

  By reacting 1 mole of this ester with at least

  6 moles of a polyamine such as diethylenetriamine at a temperature of

  from 130 to 1800C, glycerol is eliminated and we obtain

  reaction products 3 moles of a mixture of hydroxy-amino-

  isomeric ethylamino amidoamines (II), II '):

  CH3 (CH2) 7CH - CH (CH2) 7CO NHCH2CH2NHCH2CH2NH2 (II)

OH NHCH2CH2NHCH2CH2NH2

or

  CH3 (CH2) 7CH - CH (CH2) 7CO NHCH2CH2NHCH2CH2NH2 (II ')

NHCH2CH2NHCH2CH2NH2

  Continuing heating at a temperature of

  at 260 ° C, there is cyclization and a hydroxyamino

ethylamino-imidazoline (III)

/ N - CH2 (III)

CH 3 (CH 2) 7 CH - CH (CH 2) 6 C

N - CH2

CH2CH2NH2

OH NH2CH2CH2NHCH2CH2NH2

  The reaction products with ammonia, aliphatic, aromatic, cycloaliphatic-substituted primary and secondary amines at C1-C20 chain lengths are

type IV hydroxyaminoamides.

CH3 (CH2) 7CH - CH (CH2) 7CO NR1R2 (IV)

OH R2NR1

  R1, R2 = H, alkyl, aryl, cycloalkyl.

  The alkyl groups may also contain hydroxy functions or ether functions as in ethanolamine,

  diethanolamine or morpholine.

  The chlorhydroxy fatty esters in which the chlorine and the hydroxyl group are attached to neighboring carbon atoms

  give by reaction with a polyamine the same products.

  However, these products are never obtained in a state of high purity because when slowly heated a mixture of 6 moles of diethylenetriamine and 1 mole of a fatty ester

  epoxidized, some of the diethylenetriamine distils with water.

  Thus, after prolonged heating, in addition to products II and III, polymers of the polyamine-polyamide type are obtained as accompanying products. These by-products may contain polyamine structures, polyamidoamine structures, and polyimidazoline structures. Training

  oligomers or polymers increases when the ratio is increased

  epoxidized ester port / polyamine. The formation of hydroxy-amino-imidazolines is limited to polyethylene-amines and polyamines which are characterized in that they carry at least one ethylene-diamine functional group with at least three hydrogen atoms attached to the two nitrogen atoms. The compounds of this group capable of giving both amidoamines and imidazolines are: ethylenediamine,

  diethylenetriamine, triethylenetetramine, tetraethylene

  pentamine, pentaethylene hexamine, and higher homologs;

  N-aminoethylpropane diamine, N, N'-diaminoethylpropane

  diamine and butane diamines, pentane diamines and hexane diamines

  with N-aminoethyl or N, N'-diaminoethyl substituents, and N-hydroxyethyl

  ethyl-ethylene-diamine. These compounds correspond to the general formulas

ral

H2NCH2CH2NHR

  R = H-, CH3-, C2H5-, C3H7-, -CH2CH2OH, - (CH2CH2NH) xH x = 1, 2, 3, 4 ... 10 or R1R2N (CH2) yNHR3

  R1 = H-, CH3-, C2H5-, C3H7-NH2CH2CH2-,

R2 = H-, CH3-, C2H5-,

  R3 = H-, CH3-, C2H5-, C3H7-, NH2CH2CH2-,

y = 2, 3, 4, 5, 6.

  Amines capable of forming amidoamines but

  imidazolines are: 1,3-diaminopropane, 1,4-diamino-

  butane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine

  (1,4-diazacyclohexane), N-aminoethylpiperazine, N-hydroxy-

  ethylpiperazine, N-aminopropyl-1,3-propanediamine, N-

  methyl-N-aminopropyl-propane-1,3-diamine, N, N-dimethylpropane

  1,3-diamine, N, N-diethylpropane-1,3-diamine, N, N-dimethyl-

  ethylenediamine, N, N-diethylethylenediamine; N-aminohexyl

  hexane-1,6-diamine. Polyamines containing other functions such as ether (O-), thioether (-S-), sulphoxide (-SO-), sulphone (-SO 2 -) and aromatic structures can also be used for condensation. R1H2N (CH2) xY (CH2) z NH2 Y = O, S, SO, SO2, C6H5 (VI) x = 2 - 10

Y = 2 - 10

  Certain hydroxyamino amidoamines or hydroxyamino

  imidazolines bearing tertiary nitrogen atoms, such as

  reaction products of epoxidized fatty esters and N, N-dimethyl

  propane-diamine-1,3 corresponding to the formula

  CH 3 (CH 2) 7 - CH - (CH 2) 7 CO NHCH 2 CH 2 CH 2 N (CH 3) 2 (VII)

3 2 7, 2 7 2 22 3 2

OH NH

CH2CH2CH2N (CH3) 2

  can be modified by a complementary reaction with an alkylating agent such as a halide, sulfate, phosphate, etc. methyl, ethyl or benzyl. The compounds obtained are called

  mono-, di-, or tri-quaternary ammonium salts. Their characteristics

  The main problem is their solubility in aqueous systems without the addition of an acid, unlike in the case of amines, amidoamines or imidazolines. An example of this type of quaternary ammonium salt is prepared by reacting one mole of the compound of formula (VII) with 4 moles of methyl chloride, giving the following structure:

  CH 3 (CH 2) 7 CH - CH - (CH 3) 7 CO NHCH 2 CH 2 CH 2 (CH 3) 3 (VIII)

1 CL-

OH + (CH3) 2Cl

CH2CH2CH2N (CH3) 3

  Cl Other modifications of hydroxyamino amidoamines

  mono-, di- or poly-amine hydroamino-imidazolines described above.

  These consist of reaction products with reactive oxiranes such as ethylene oxide, propylene oxide or butylene oxide. The reaction occurs initially on the primary and secondary nitrogen atoms, that is to say the nitrogen atoms

  connected to one or two hydrogen atoms by covalent bonds.

  The reaction products belong to the class of N-hydroxy-

  ethyl-, N-2-hydroxypropyl- and N-2-hydroxybutyl-hydroxy-amino-amidoamines or -hydroxyaminoimidazolines. If an excess of the oxirane is reacted, polyethylene oxides, polypropylene oxides or polybutylene oxides are obtained. In

  in this case, the hydroxyl groups also react.

  The use of polyamine reaction products with epoxidized unsaturated oils or esters as emulsifiers for asphalts and more specifically as emulsifiers for solvent-free asphalt emulsions and emulsions for coating application

  suspension, has never been previously described.

  Reaction products of diethylenetriamine, dipropylenetriamine and other polyamines with epoxidized linseed or soybean oil are described as polyamide prepolymers useful as adhesives or resin hardeners in the following patents : French Patent 1,164,471, United States Patent 2,890,228, French Patent 1,295,619, British Patent 953,422, United States Patent 3,291,764, RDA Patent 50,750, Patents British Patent Nos. 816,986 and 811,797, United States Patents 3,035,000 and 3,112,294, GDR Patent No. 56,934, Japanese Patent 75,539,999, Patent Application

FRG 2,420,254.

  Similar condensates are described as agents

  emulsion breakers for water-in-oil type oil emulsions

  the oil in U.S. Patent No. 3,148,199 and as growth inhibitors for sulfate reducing bacteria

  in U.S. Patent 3,049,992.

  The examples which follow illustrate the invention without, however, limiting its scope; in these examples, the indications of parts and percentages are by weight unless otherwise indicated

opposite.

  In these examples, emulsifiers used to obtain cationic asphalt emulsions in water, which can be used for blending with water, are described.

  shearing with various silicate and limestone aggregates.

  After rupture (evaporation of water), asphalt films

  have excellent adhesion to the surface of the aggregate.

  Particularly satisfying results are obtained.

  with the reaction products of epoxidized linseed oil,

  epoxidized soybean oil or esters of tall oil fatty acids

  epoxidized with ethylene diamine, diethylenetriamine,

  triethylenetetramine and higher homologs or with amino

  ethyl-piperazine, hydroxyethyl-piperazine, N-aminoethylethanol-

  amine, dipropylene triamine and any mixtures of these amines. For the preparation of the bituminous emulsions according to the invention, it is intimately mixed under high shear in

  a colloidal mill an acidic aqueous solution of emulsifiers

  the following description. The bitumen content can range from 80% by weight and is preferably 60 to 70%. The amount of the emulsifying agent can represent from 0.1 to 10% of the weight of the emulsion, and it is preferably from 0.3 to 1.5% of this weight. Depending on the nature of the emulsifying agent, a quality emulsion is obtained for mixing at a pH range of 2 to

  7, with the best results at a pH of about 3.

  The "bitumen" used in the emulsion may be from crude oil from the United States of America or elsewhere; it may be a bitumen, a natural asphalt, a petroleum oil, an oil residue of road pavement quality, a plastic residue from the distillation of coal tar,

  oil pitch and asphalt cements diluted by

  (fluxed asphalts). We can emulsify with agents

  emulsifiers according to the invention, an asphalt cement with a viscosity

  practically any degree of penetration for use

  in the construction of road surfaces, as described

  in the United States of America ASTM D-3381 and D-496.

  The solutions of cationic emulsifiers will normally be obtained by suspending the amidoamine or imidazoline in water to which an appropriate acid is added, for example hydrochloric acid, sulfuric acid or phosphoric acid. or a like acid in an amount sufficient to achieve the desired pH of less than 7; a clear emulsifier solution is thus obtained. The emulsifying agent solution is then heated to about 55 ° C. and the fluid asphalt heated to

  precondition at 120-125 C are then mixed under high shear

  in a colloid mill for 30 seconds; we obtain

  brown-colored asphalt emulsions with a creamy texture.

  Before submitting to tests according to United States of America standard

  ASTM D-244, the emulsions are stored at 70 ° C. for 16 hours.

  Aggregate mixing tests were carried out by placing a determined weight of the granulate in a mixing bowl, adding 5 to 10% by weight of the emulsion to the granulate and mixing for 1 to 5 minutes. The mixture is divided into three equal parts and placed in three cups. The first sample is set aside; the second sample is washed with water immediately after

  mixture and the third sample is washed with water after

  vation for 1 hour. The percent coating of the aggregate surface is directly visualized by visual inspection. On the first sample, the initial coating is determined on

  the second sample the coating after washing and on the third

  sth sample the coating after one hour preservation and washing. The coating requirements in the construction industry are respectively 95% minimum, 50% maximum,

and 50% minimum.

  The aggregates of the road-surfacing mixtures according to the invention are dense aggregates of such dimensions that the whole passes through a sieve having a mesh size of 4.76 mm and at least 80% is retained.

  on the sieve with a mesh size of 0.074 mm.

  Aggregate mixing tests are carried out by

  mixing the granulate with water and the aqueous bituminous emulsion. Additive mineral fillers such as

2577 566

  only portland cement, hydrated lime, limestone powder and fly ash to shorten the break-up time; and salts such as ammonium sulphate, or emulsifiers to retard the breakdown of the suspended system. These additives must comply with the requirements of US ASTM D-242. These materials are mixed in a bowl of

  mixing until a homogeneous suspension is obtained. The impossibility

  The ability to form a stable suspension within 3 to 4 minutes of mixing when correct proportions of each component have been used indicates that the components of the mixture are incompatible. This preparation of the mixture is necessary to simulate the real conditions of application. After mixing the slurry, it is spread in a mold placed on an asphalt felt and the breaking time is measured by applying a paper towel to the exposed surface of the slurry. If there is no transfer of a brown stain on the paper towel, the suspension is considered

  like "broken". We could also measure the duration of hardening

  using a cohesion test device. Many

  other tests as described in the United States of America standard.

  ASTM D-3910 is used to measure the mechanical strength and other physical properties of the dispersion. To establish the qualities of the coating applied in suspension, use the Performance Guide for Slurry Seal published by Asphalt Emulsion

  Manufacturers Association of the United States of America.

  The emulsion must be stable during mixing and must break within the expected time after application. The agents

  emulsifiers according to the invention give very satisfactory results.

  doing without auxiliary emulsifying agents. For example, the times of rupture can be controlled by the concentration of the emulsifying agent, the addition of lime, cement or other mineral additive or an organic additive which modifies the

  breaking characteristics of the suspended system. We can also

  use an organic polymer latex to reinforce the

  gangue. The organic additive is preferably added. to the suspension

granulation-emulsion.

  The emulsifying agents according to the invention

  very satisfactory results without emulsifying agents

  iliary. However, occasionally, it may be necessary

  to modify the properties of the emulsion in order to improve the

  cosity to a certain asphalt content or to improve the dust and fines stability existing on the granulate, in order to prolong or shorten the breakage time, etc. In these cases, one of two processes can be exploited. Alternatively, a mixture of tall oil fatty acid, preferably tall pitch, is added to the bitumen (asphalt) before emulsification. in order to improve the rupture or to improve the viscosity of the emulsion, or the mixtures of the amidoamines and imidazolines described above are used to emulsify the bitumen.

  with cationic or nonionic emulsifiers

  patible. Auxiliary emulsifiers which can represent up to 90% of the total emulsifier composition,

  are fatty amines, fatty propane-diamines, amido

  fatty amines and fatty imidazolines.

  With this class of compounds, we observe in general

  a decrease in the break time. Other emulsifying agents

  are monoquaternary ammonium

  fatty diquaternary diammonium salts and emulsifiers

Nonionic polymers such as polyethers of ethylene glycol and nonyl or dodecyl phenol. Combinations with amidoamines or imidazolines, based on fatty monocarboxylic acids from various sources or C19 and C21 dicarboxylic acids, C22-tricarboxylic acids or sulfonated tall oil fatty acids described in US Pat. In America 4,447,269, 4,450,011 and 4,462,840 may also be used. These mixtures can also be obtained by premixing the epoxidized oils with these acids and reacting the mixtures with a polyamine. Suitable monocarboxylic acids for this purpose are tall oil fatty acids, crude tall oil, resin acids, rosin condensed with fumaric acid or maleic acid, tall oil pitch, fatty acids. of tallow, soybean fatty acids, similar raw materials. It is also possible to react together with lignin of the process

Kraft or Vinsol.

  Cationic acids which are long chain C 3 aliphatic carboxylic acids obtained by dimerization of fatty acids from various sources can also be reacted together. A product of this type is sold commercially by Emery Industries, Inc. under the brand name "Empol Dimer Acids". The emulsions prepared using the epoxidized-polyamine oil condensates according to the invention are stable and can be

  kept for long periods of time until the moment of use.

  tion. Depending on the type of granulate and its cleanliness, the mixture is improved by pre-moistening the granulate with I to 5% of its weight of water when it is. intended to be mixed with

  quality emulsions for solvent-free mixing. We can also

  improve, when necessary, the mixing and breaking characteristics (high percentage of coating after one hour of storage and washing) of the cationic asphalt emulsions by adding to the asphalt, before the emulsification of I to 15 Z of its weight of a solvent such as a diesel oil. Emulsions

  prepared with the di- and tri-carboxylic acid condensates

  Polyamines according to the invention are stable and can be stored for a long time until the moment of use. Depending on the intended application, the emulsion can be mixed with the granulate in a central mixing plant in a large bowl mixer and transported to the site of use. But we can also transport the emulsion to the site of use and mix

  at this point either with a mixing device such as a

  motor mixing valve, either by hand.

  In cases where the emulsions prepared using the emulsifying agents according to the invention are used in suspension roadway applications, the granulate is pre-moistened with 1 to 15% water, depending on the climatic conditions. If desired, additives such as aluminum sulphate may be added to the water, or granular cement or hydrated lime may be mixed with the granulate in order to obtain granulate-emulsion suspension mixtures having Characteristics

  of mixing and the desired break times.

  In the examples which follow and which illustrate the practice of the invention, the preparation of various types of emulsifying agents according to the invention is described and the advantages of the use of these compounds in a cationic bituminous emulsion of the quality for mixing at medium break. EXAMPLE 1 In this example, it is shown that from the same raw materials, at various temperatures and with varied ratios between reagents, various emulsifiers can be obtained. Emulsifier A 100 parts of the commercial product Epoxol 9-5 (epoxidized linseed oil from Swift Technical Products) are mixed with 50 parts of diethylenetriamine and heated slowly to 260 ° C. All the condensate is collected, cools

  and diluted to 50% active ingredient with isopropanol.

  Emulsifying agent B 100 parts of Epoxol 9-5 are mixed with 50 parts of aminoethylethanolamine and heated to 225.degree.

  the condensate, the reaction is stopped and cooled.

  Emulsifier C 300 parts of the commercial product Flexol EPO (epoxidized soybean oil from Union Carbide Corporation) and 250 parts of ethylene diamine are mixed at room temperature and slowly heated to 220 ° C. After harvesting all water of

  reaction and excess ethylene-diamine, cool to

  ambient temperature and diluted with isopropanol in sufficient

  to obtain a fluid product.

  Emulsifier D 200 parts of Flexol EPO and 100 parts of diethylenetriamine are mixed at room temperature and heated to 265 C. When all the distillate has been collected, the mixture is cooled and the isopropanol is added in sufficient quantity to obtain

fluid product.

Emulsifying agent E

  200 parts of the product are mixed at room temperature

  commercial grade Flexol EP-8 (dioctyl ester of epoxidized oil)

  Union Carbide Corp.) and 100 parts of diethylene

  triamine and slowly heated at 225 ° C. for 30 minutes. when

  collected all the distillate, cooled.

  Emulsifying agent F 200 parts of the commercial product Epoxol 9-5 and 100 parts of dimethylamino-propylamine are mixed and heated to 210 ° C.

  until all the distillate has been collected.

  Emulsifying agent G 200 parts of the commercial product Epoxol 9-5 are heated with 100 parts of diethanolamine at 225.degree. C. After cooling, 50 parts of diethylenetriamine are added per 100 parts of the condensate and the mixture is heated to 210.degree. of the entire distillate. Emulsifying Agent H 40 parts of the commercial product Epoxol 9-5 are mixed with 40 parts of the commercial product Rosin S and 50 parts of diethylenetriamine. This mixture is heated slowly to 270 ° C until all the distillate is collected. It is allowed to cool and is diluted with isopropanol in an amount sufficient to obtain a

fluid reaction product.

  Emulsifier I One hundred parts of Epoxol 9-5 are mixed with 100 parts of tall oil fatty acids (L-5) and 200 parts of a mixture of amines containing aminoethylpiperazine, triethylene tetramine and aminoethylethanolamine. We heat to 2250C until harvest of

the entire distillate.

  Emulsifier J 200 parts of Flexol EPO are mixed with 100 parts of aminoethylpiperazine and heated to 260.degree.

  all of the distillate is cooled and diluted with isopropanol.

Exempt 2

  Aqueous-bituminous emulsions are prepared

  with each of the emulsifiers A to E of Example 1 and blending with dense aggregates for each of these emulsions, as described above.

  In the first place, aqueous emulsions are

  cationic asphalts with asphalts varied to 64% asphaltic residue, 1.5% emulsifier at pH 2.5 and water in 100% count (these percentages relate to

weight of the emulsion).

  Suspensions are then prepared by adding to 100 g of Camak granulate (granite crushing sand), 16% of the cationic aqueous-bituminous emulsion, 10 to 14% of water and 0 or 1% of portland cement as breakthrough accelerator or 0.05% aluminum sulphate as a breaking retarder

  (these percentages relate to the weight of the aggregate).

  For all the emulsifiers tested, without additive or with the retarding agent, mixtures are obtained in stable homogeneous suspension in one minute of mixing, unless otherwise specified. With an addition of 1% cement

  mixture, the suspensions are only stable for 30 to 50 seconds.

  EXAMPLE 3 In this example, the short break times of the suspensions prepared in Example 2 are demonstrated, as well as the possibility of acting on the breaking times by the addition of a mineral filler (portland cement). The times of rupture of the suspensions are determined by means of the test procedure

  described above, that is to say by applying a napkin

  pier on the exposed surface of the suspension spread in a mold on a bituminous cardboard. If there is no transfer of a stain

  brown on the paper, the suspension is considered broken.

  The breaking times are reported in Table I below.

Table I

  Suspension rupture time, min. Agent Arulfide Sulfate-Cement-free minium, additive Asphalt additive 0.5% 1.0% 0.05%

  A Exxon (pen 120-150)> 60 10 rupture * -

B Exxon AC-20> 60 3 -> 60

C Arco AC-20> 60 2 break * -

  Db Conoco AC-20> 60 6 rupture *> 60 E Chevron AC-20 rupture * rupture * -> 60 * The suspension breaks before the expiration of the mixing time

of a minute.

Example 4

  In this example, it is shown that the emulsions prepared using the emulsifiers according to the invention have the qualities required for mixing without the addition of solvents. To highlight the various possibilities of use of these emulsions,

  mixed aggregates were used in the blending tests -

  siliceous and limestone. The emulsions were prepared with various asphalts at contents of 64 to 69% of asphalt residue. We have

  obtained excellent emulsions with proportions of emulsified agents -

  from 0.8 to 1.5%. The emulsions were prepared in the pH range of 2.5 to 4.0. PH adjustments were made with dilute hydrochloric acid. The results of the tests are

  reported in Table II below. The test with aggregates

  whether or not an emulsion is suitable for mixing operations.

  It was done with a bowl of mixture and a spoon. According to the state of cleanliness of the granulate, it was previously moistened with 1 to 3% water before adding the emulsion. After mixing 5 to 9 g of an emulsion (per 100 g of granulate) with the granulate for 1 minute, the initial coating, the coating after the initial wash and the coating after storage for 1 hour and washing were visually determined. . The results obtained make it possible to determine the mixing efficiency and the breaking strength with a granulate

particular.

Table II

  Properties of asphalt emulsions

_- ,,,. ,, _ _

  % after washing at the end of emulsifying agent. Attractive coating Asphalt% initial pH,% I min 30 min 60 min Aggregate A Exxon pen. 1.0 2.5 100 5 50-Mixed granulate 1) -150 A Exxon pen. 1.5 2.5 100 0 10 95 Tennessee Limestone -150 5 30 50 Tennessee River Gravel C Exxon pen. 1.0 4, 0 100 30 100 100 Mixed granulate1) -150 D Exxon pen. 1.0 2.5 100 5 100 100 Mixed Granules1) -150 E Chevron 1.5 2.5 100 0 30 90 Mixed Granulary1) AC-20 F Arco AC-20 1.5 2.5 100 0 30 80 Mixed Granulat1 ) G Exxon AC-20 1.5 2.5 100 0 90 100 Tennessee Limestone 5 100 100 Tennessee River Gravel LnI,. ,, Vl o 'Table II (continued)% after wash after

EmuL agent- Coating _...

  Suction Asphalt% initial pH,% 1 min 30 min 60 min Granulat H Exxon pen. 1.5 2.5 100 0 20 30 Tennessee Limestone6 -150 0 80 100 Tennessee River Gravel H Exxon pen. 1.0 2.5 100 5 75 - Mixed Granules1) 150 1) I Chevron 1.5 2.5 100 0 20 50 Mixed Granules1) AC-20 J Conoco 1, 5 2.5 100 O 10 95 Tennessee Limestone AC -20 5 30 50 Tennessee iR River Gravel J Exxon pen. 1.0 2.5 100 2 70 - Mixed granulate1) -150

  1) Mixed granulate consisting mainly of limestone chips and granite and fine gravel.

  -4 μl Ln 0s For all the emulsifying agents tested, excellent coating characteristics are observed with all

types of aggregates.

  It is clear that the invention is in no way limited to the preferred embodiments described above as examples and that one skilled in the art can make modifications thereto.

  varied without departing from its scope.

R EV IN D I C AT I 0 N S

  A cationic bituminous emulsion containing from about 80% by weight of bitumen and characterized in that it contains from about 0.1 to 10% by weight of an emulsifying agent selected from the group consisting of reaction products of a polyamine with a compound of the group consisting of unsaturated fatty acids epoxidized at chain lengths of C8 to C22 and their esters, the complement at 100% by weight consisting of water and the emulsion

having a pH of 2 to 7.

  2. Emulsion according to claim 1, characterized in that

  that the polyamines are selected from the group consisting of

  Lene diamine, diethylenetriamine, triethylenetetramine,

  tetraethylene pentamine, aminoethylethanolamine, aminoethyl-

  piperazine and hydroxyethyl piperazine.

  3. Emulsion according to claim 1, characterized in that

  up to 90% of the emul-

  total, one or more auxiliary emulsifiers

  selected from the group consisting of fatty amines, propane-

  fatty diamines, fatty amidoamines, fatty imidazolines,

  amidoamines or imidazolines prepared from dicarboxylic acids

  C19-C21 boxyl, C22 tricarboxylic acids or sulfonated tall oil fatty acids, fatty monoquaternary ammonium salts, diquaternary diammonium salts and polyethers of

  ethylene glycol and nonyl or dodecyl phenol.

  4. Emulsion according to claim 1, characterized in that

  up to 90% of the emul-

  total, one or more auxiliary emulsifiers selected from the group consisting of nitrogen derivatives of

  resins and nitrogen derivatives of kraft lignin.

  5. Emulsion according to claim 1, characterized in that

  that the emulsifier has been prepared by reacting a potash

  amine with a mixture of sulphonated tall oil fatty acids, fatty mono-, di- or tri-carboxylic acids and an epoxidized compound such as

  as defined in claim 1.

  6. Emulsion according to claim 1, characterized in that the emulsifying agent has been prepared by reaction in common of a potyamine with a mixture of resin acids and one or more

  epoxidized compounds as defined in claim 1.

  Emulsion according to Claim 1, characterized in that the emulsifying agent has been prepared by reaction in common of a polyamine with a mixture of kraft lignin and one or more

  epoxidized compounds as defined in claim 1.

  8. Emulsion according to any one of claims 1

  at 7, characterized in that it contains from about 60 to 70% by

  weight of bitumen, from about 0.3 to 1.5% by weight of emulsifying agents.

  in relation to the weight of the emulsion, and water in addition

  at 100% by weight, the emulsion being at about pH 3.

  9. Emulsion according to claim 1, characterized in that

  that it also contains from 1 to 15% by volume of a hydro-

  carbon. 10. Emulsion according to claim 1, characterized in that added to the bitumen, before emulsification, a mixture

of tall oil fatty acids.

  11. Emulsion according to claim 10, characterized in that

  that the tallt-oiL fatty acid mixture consists of tall oil pitch.

  Emulsion according to Claim 1, characterized in that the esters are chosen from the group consisting of oils

  vegetable and animal fats.

  13. Mixture for road surfacing by suspension, consisting of a cationic aqueous-bituminous emulsion and an inorganic granulate and suitable for application, characterized in that it comprises: a dense mineral granulate passing through a sieve to mesh aperture of 4.76 mm with at least 80% retained on a sieve with a mesh size of 0.074 mm; from about 8 to 20% of an oil-in-water emulsion, based on the weight of the inorganic aggregate, said emulsion comprising from about 5 to 65% of bitumen based on its total weight, of about 0.5 to 2% of a cationic emulsifier selected from the group consisting of

  reaction products of a polyamine with a member of the group

  consisting of unsaturated fatty acids epoxidized at lengths of

  C8 to C22 chains and their esters, relative to the weight of the emulsion

  addition of water to complement 100% of the weight of the emulsion, the latter having a pH of 2 to 7; from about 4 to 16% water relative to the weight of the mineral aggregate, added to form a

  suspension of the granulate and the emulsion; and up to 3% of an addi-

  mineral or organic tif used to shorten the break time of the mixture. 14. Mixture according to claim 13, characterized in that it contains from about 55 to 65% of bitumen, relative to the weight of the emulsion, from about 0.5 to 2.0% of emulsifying agent, relative to the weight of the emulsion, and water to complement 100 X

  by weight, the emulsion being at a pH of about 2.5.

  15. Mixture according to claim 13, characterized in that before the emulsification, a mixture is added to the bitumen.

of tall oil fatty acids.

  Mixture according to claim 15, characterized in that

  the mixture of tall oil fatty acids consists of tall oil pitch

  oil. 17. Mixture according to claim 13, characterized in that

  that the polyamines are selected from the group consisting of

  ethylene diamine, diethylene triamine, triethylene tetramine,

  tetraethylene pentamine, aminoethylethanolamine, aminoethyl-

  piperazine and hydroxyethyl piperazine.

  18. Mixture according to claim 13, characterized in that the mineral additive is chosen from the group consisting of cement

  portland, hydrated lime, limestone powder and ashes

  lants, or ammonium salts and sulphate, aluminum sulphate, ferric chloride, etc. 19. Mixture according to Claim 13, characterized in that the esters are chosen from the group consisting of oils

  vegetable and animal fats.